CN103904277B - Polyolefin-based porous film - Google Patents

Polyolefin-based porous film Download PDF

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Publication number
CN103904277B
CN103904277B CN201410131516.XA CN201410131516A CN103904277B CN 103904277 B CN103904277 B CN 103904277B CN 201410131516 A CN201410131516 A CN 201410131516A CN 103904277 B CN103904277 B CN 103904277B
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perforated membrane
polyolefin
stretch
reel
porous film
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CN103904277A (en
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伊东己行
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Asahi Kasei Corp
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Asahi Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to the polyolefin-based porous film formed by polyolefin resin composite, its aperture surface area is 35.0 ~ 42.0m 2/ g and birefringence is 2.0 × 10 -2~ 4.0 × 10 -2.

Description

Polyolefin-based porous film
The divisional application that the application is the applying date is on November 25th, 2011, application number is 2011800627351, denomination of invention is the application of " polyolefin-based porous film and manufacture method thereof ".
Technical field
The present invention relates to polyolefin-based porous film, be especially suitable as polyolefin-based porous film and the manufacture method thereof of battery separator.
Background technology
The mechanical property of polyolefin-based porous film, the excellence such as chemical-resistant and electrical characteristics, therefore for packaging material purposes, medical usage and electric material purposes etc.Wherein, in battery use, utilize and only make the function of the separator of ion permeable as being separated with negative pole by positive pole and being used for preventing the cutting function of inside battery high temperature, cell reaction danger out of control (making the function of hole obturation at the temperature lower than thermal runaway temperature), be useful in the design of safer secondary cell.
If roughly divide the manufacture method of polyolefin-based porous film, can list and carry out the damp process of porous with abstraction process and carry out dry process (also known as stretching perforate method) two kinds of methods of porous with stretching process.
As the former manufacture method, include, for example out the method recorded in patent documentation 1.Disclose following manufacturing technology in patent documentation 1: for add in polyethylene plasticizer (DOP) and silicic acid particulate, melting mixing, extrude after in extraction tank, extract plasticizer and silicic acid particulate and porous, the wet type film that is made up of three kinds of compositions, by birefringence is set as 1.0 × 10 -3above, mechanical strength (hot strength, tensile modulus of elasticity) is improved.
On the other hand, as the manufacture method of the latter, such as, the method recorded in patent documentation 2 ~ 5 can be listed.Patent Document 2 discloses the manufacture method of polyethylene porous membrane, according to the document, disclose the reel (below also known as " atresia reel ") before offering hole along MD(MachineDirection) cold stretch, then along the basic technology of MD hot-stretch.Patent Document 3 discloses the blow-up ratio in the blow molding method using annular die head and the relation of various physical property.Patent Document 4 discloses and be less than the ethylene-propylene rubber (EPR) of 10 quality %, the technology of Ethylene-Propylene-Diene rubber (EPDM) to improve mechanical strength interpolation.Patent Document 5 discloses by polypropylene (PP) and polyethylene (PE) is formed, the laminated porous film that is laminated into 3 layers (PP/PE/PP), also disclose and the birefringence of the poly atresia reel before stretching be set in 2 × 10 -2~ 4 × 10 -2scope in, comprise the various physical property of the aperture surface area of gained laminated porous film.In patent documentation 6, reduce the technology of restoring as the film width will occurred because of MD hot-stretch, disclose laminated porous film perforated membrane being formed as 3 layers (PP/PE/PP), use the material of composition as perforated membrane of isotactic polypropylene and random polypropylene.In patent documentation 7, as the manufacture method of biaxial stretch-formed perforated membrane using dry process, disclose the technology of perforated membrane that known longitudinal uniaxial tension obtains by limit longitudinally hot wire-CVD limit cross directional stretch.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 58-197659 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 58-59072 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2001-122998 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2003-192814 publication
Patent documentation 5: Japan Patent No. 3003830 publications
Patent documentation 6: Japanese Unexamined Patent Publication 11-297297 publication
Patent documentation 7: International Publication No. 2007/098339 pamphlet
Summary of the invention
the problem that invention will solve
But, the polyolefin-based porous film obtained in method according to patent documentation 1, owing to being Extraction solvent and obtain the method for perforated membrane in the reel that obtained by extrusion molding, in its operation, do not comprise stretching process, therefore, the average pore size of gained perforated membrane is little, there is no sufficient resistance, in addition, due to needs abstraction process, therefore there is shortcomings such as producing rate variance.In addition, about the perforated membrane recorded in patent documentation 2 ~ 6 or the perforated membrane obtained by the method recorded in patent documentation 2 ~ 6, also there is the problem that can not obtain sufficient resistance.In addition, the method recorded in patent documentation 7 owing to carrying out longitudinal relaxation (contractions) thus speed of production reduction when cross directional stretch simultaneously, and due to cross directional stretch need special while biaxial stretcher, there is the shortcomings such as equipment cost is excessive thereupon.
In recent years, as hybrid vehicle (HEV), the upper battery carried of electric automobile (EV), carry out the research of the lithium rechargeable battery of Miniaturizable energetically, therefore safe, reliability and high output, the contour performance-based of high capacity, and require the separator that resistance (the easily property passed through of ion) is lower.But generally speaking, falling in low-resistance situation, proof voltage and mechanical strength reduce simultaneously, have the problems such as the short circuit thus easily between generating electrodes, this problem is the problem of waiting until solution, especially for high performance lithium ion secondary battery.
In addition, in dry process, when in order to improve the productivity ratio of film and the high speed that stretched by MD etc., also there is the problem that can not obtain the polyolefin-based porous film with sufficient gas permeability.
The object of the invention is the excellent productivity utilizing dry process, the polyolefin-based porous film with excellent resistance (ion permeability), gas permeability, proof voltage and mechanical strength is provided.
for the scheme of dealing with problems
In order to reduce the resistance of polyolefin-based porous film (hereinafter also referred to as " perforated membrane "), usually adopting and improving stretching ratio etc. and the method that increases porosity.But, in the method, compromise proof voltage and mechanical strength, be difficult to provide the perforated membrane being suitable for practicality.Further investigate to solve this problem, found that, the aperture surface area of polyolefin-based porous film and birefringence are set in specific scope, or the birefringence of atresia reel (before annealing in process) being set as specific value makes the aperture surface area of gained polyolefin-based porous film be particular range while above, by adopting at least one in aforesaid way, the balance of resistance (ion permeability), proof voltage and mechanical strength is improved.
In addition, the present inventor etc. further investigate to manufacture the much higher pore membrane of gas permeability by dry process with high production rate, result is found out, MD is stretched high speed time the gas permeability of perforated membrane that an occurs main cause reducing be that the aperture of the Width (TD) of the film caused because film width reduces diminishes.And understood fully, reduce adjoint gas permeability to prevent this film width and reduce, effectively, stretched by TD and the film width of the minimizing because MD stretches is replied.
And specify that if with reference to technology general knowledge be the beyond thought fact: when being set to draft temperature now lower than common draft temperature, obtain the perforated membrane shrinking little dimensional stability and improve.
Further discovery, after above-mentioned TD stretching process, when carrying out heat setting at the temperature higher than TD draft temperature, obtains the perforated membrane with highly-breathable and the dimensional stability in the past do not had, thus completes the present invention.
That is, the 1st execution mode of the present invention is as described below.
A manufacture method for polyolefin-based porous film, it comprises following operation successively:
(A) operation: by the reel molding procedure of the shaping atresia reel of polyolefin resin composite;
(B) operation: by the MD cold stretch operation of extruding direction (MD) cold stretch and porous of the atresia reel obtained in (A) operation along described reel under-20 DEG C ~ (Tm-30) DEG C (Tm is the fusing point (DEG C) of atresia reel);
(D) operation: will through the film of (B) operation along the TD cold stretch operation perpendicular to direction (TD) cold stretch of MD; And
(H) operation: heat-setting procedure,
(H) the heat-set temperature T in operation 2(DEG C) meets following formula (1) and (2).
T 2>T 1（1）
（Tm-3）≥T 2≥（Tm-40）（2）
In formula, T 1represent the draft temperature (DEG C) in (D) operation, Tm represents the fusing point (DEG C) of atresia reel.
2nd execution mode of the present invention is as described below.
A kind of polyolefin-based porous film, it is the polyolefin-based porous film formed by polyolefin resin composite, and its aperture surface area is 35.0 ~ 42.0m 2/ g and birefringence is 2.0 × 10 -2~ 4.0 × 10 -2.
3rd execution mode of the present invention is as described below.
A manufacture method for polyolefin-based porous film, it comprises each operation of following (A) and (B):
(A) operation: by the reel molding procedure of the shaping atresia reel of polyolefin resin composite;
(B) operation: by the MD cold stretch operation of extruding direction (MD) cold stretch and porous of the atresia reel obtained in (A) operation along described reel under-20 DEG C ~ (Tm-30) DEG C (Tm is the fusing point (DEG C) of atresia reel);
Wherein, the birefringence of the atresia reel obtained in (A) operation is 3.0 × 10 -2above, the aperture surface area of gained polyolefin-based porous film is 42.0m 2/ below g.
the effect of invention
According to the of the present invention 1st and the 2nd execution mode, the polyolefin-based porous film of the physical property balancing good of resistance, proof voltage and mechanical strength can be provided.
According to the 3rd execution mode of the present invention, the polyolefin-based porous film of gas permeability and excellent in dimensional stability can be manufactured with high production rate.
Accompanying drawing explanation
Fig. 1 is the key diagram of the manufacture method of the sample melting and use in short circuit test.
Fig. 2 is the sectional view of the sample when melting and use in short circuit test.
Figure 3 shows that the schematic diagram that device when carrying out fusing and short circuit test is formed.
Figure 4 shows that the figure of the concrete example of the order of each operation of the manufacture method of present embodiment.
Embodiment
Be described in detail to for implementing embodiments of the present invention (hereinafter referred to as " present embodiment ") below.But, the invention is not restricted to following execution mode, can implement with various distortion in the scope of its main idea.
(polyolefin resin composite)
In the present embodiment, polyolefin resin composite refers to polyolefin-based resins itself or the composition containing polyolefin-based resins, the ratio of the resin total amount that polyolefin-based resins accounts in polyolefin resin composite is preferably more than 50 quality %, be more preferably more than 80 quality %, be more preferably more than 90 quality %, more preferably more than 95 quality %.
In addition, polyolefin-based resins refers to containing the polymer of alkene as monomer component.Herein, polyolefin-based resins, except the polymer only formed by alkene, also comprises the copolymer of the monomer beyond alkene and alkene, in this case, the copolymerization ratios of olefin unit is preferably more than 90 quality %, is more preferably more than 95 quality %, more preferably more than 99 quality %.
The melt flow index (hereinafter referred to as MI) of said polyolefins system resin is preferably 0.05 ~ 3g/10 minute, is more preferably 0.1 ~ 2g/10 minute, more preferably 0.2 ~ 1g/10 minute.When the MI of polyolefin-based resins is more than 0.05g/10 minute, easy enforcement melt extrudes the traction under shaping and high draw ratio, and time below 3g/10 minute, the birefringence of atresia reel (orientation) can be brought up to specific scope, thus, gained perforated membrane forms the tight pore structure of small-bore, obtains the effect improving proof voltage and mechanical strength.
Be not particularly limited the polyolefin-based resins used in present embodiment, such as, can list polyethylene, polypropylene, wherein, high density polyethylene (HDPE) is owing to having excellent stretching opening, productivity ratio and preferably using.Therefore, polyolefin resin composite preferably contains high density polyethylene (HDPE) as principal component." contain as principal component " herein and refer to, polyolefin is more than 80 quality % relative to the ratio of the total amount of all resins contained in polyolefine resin composition, is preferably more than 90 quality %, is more preferably more than 95 quality %.
The preferable range of the density of high density polyethylene (HDPE) is 0.958 ~ 0.965g/cm 3, be more preferably 0.959 ~ 0.964g/cm 3, more preferably 0.960 ~ 0.963g/cm 3.By density is set as 0.958g/cm 3above, opening becomes good, and gas permeability and resistance all become good.On the other hand, by density is set as 0.965g/cm 3below, the reduction of mechanical strength can be alleviated.
As above-mentioned polyethylene, Natene and ethylene copolymer can be listed.
In ethylene copolymer, as the olefinic comonomer composition except ethene composition, include, for example out propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene or 1-decene etc., the content of the comonomer components except ethene composition is preferably less than 10 % by mole, in order to obtain the degree of crystallinity being most suitable for stretching perforate, be more preferably less than 5 % by mole, more preferably less than 2 % by mole.In addition, its structure can be any one of block copolymer or random copolymer.
In addition, above-mentioned poly weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) affect the birefringence (orientation) of perforated membrane, and result also will have influence on mechanical strength, proof voltage.More particularly, by the birefringence of this perforated membrane is set as specific scope, define the perforated membrane of proof voltage and mechanical strength, the condition of the annealing in process, stretching etc. that apply atresia reel is being set to a timing, the birefringence of the atresia reel that the factor controlling the birefringence of perforated membrane was obtained by the extrusion molding stage decides.That is, if the birefringence of atresia reel is comparatively large, then the birefringence of gained perforated membrane also becomes large.
And, as the factor of the birefringence of left and right atresia reel, except condition of molding, the poly weight average molecular weight and molecular weight distribution that form and contain in the polyolefin resin composite of atresia reel can be listed.Wherein, the preferable range of weight average molecular weight is more than 100,000, is more preferably more than 150,000, is also more preferably more than 180,000, more preferably more than 200,000.Can obtain the atresia reel of high orientation thus, the birefringence of result perforated membrane also can be set to specific scope, result, defines the tight pore structure of small-bore, and the proof voltage of perforated membrane and mechanical strength (such as piercing through intensity) improve.
Wherein, as the upper limit of weight average molecular weight, from the viewpoint of extrusion molding, be preferably less than 400,000, be more preferably less than 200,000, more preferably less than 250,000.
In addition, in the present embodiment, molecular weight distribution is not particularly limited, can be such as about 3 ~ 50 scope in, by increase molecular weight distribution, further can improve the birefringence of perforated membrane, therefore, molecular weight distribution is preferably more than 8, is more preferably more than 10, and more preferably more than 13.
Wherein, in this manual, weight average molecular weight (Mw) and number-average molecular weight (Mn) are the values that the GPC method (gel permeation chromatography) by taking polystyrene as standard substance obtains.
As above-mentioned polypropylene, from the viewpoint of stretching opening, the percentage of preferred isotaxy five unit group is the isotactic homo-polypropylene of more than 95%.Wherein, the isotaxy five unit group percentage in polypropylene constituent is that five adjacent methyl are all in the ratio of unidirectional chain (mmmm) relative to polypropylene molecular chain entirety, as with 13(mmmm) peak percentage in whole absworption peaks in the methyl carbon region that C-NMR measures is obtained.In addition, according to A.Zambellietal., (Macromolecules8,687 (1975) process the ownership of the signal in the methyl region containing isotaxy five unit group.
Consider TD cold stretch, mechanical strength, mouldability etc., polyacrylic weight average molecular weight (Mw) is preferably 300,000 ~ 1,000,000, is more preferably 400,000 ~ 900,000, and more preferably 500,000 ~ 800,000.In addition, the molecular weight distribution (Mw/Mn) obtained by weight average molecular weight (Mw) and number-average molecular weight (Mn) is not particularly limited, such as, can be 3 ~ 50.
In polyolefin resin composite except above-specified high density polyethylene, isotactic homo-polypropylene also can other polyolefin-based resins, various elastomer classes etc. blended material modified.
As other polyolefin-based resins, such as, poly-1-butylene, poly-4-methyl-1-pentene, ethene-α polyolefin copolymer etc. can be listed.
In addition, during with above-mentioned high density polyethylene (HDPE) for principal component, low density polyethylene (LDPE), polypropylene etc. can be listed.During with isotactic homo-polypropylene for principal component, can list high density polyethylene (HDPE), low density polyethylene (LDPE), containing the comonomer components such as ethene random/block polypropylene etc.
In addition, as various elastomer class, include, for example out ethene based elastomers such as SEBS, SEPS etc. and ethene-α polyolefin copolymer closes elastomer.
These other vistanex, material modifiedly can be used alone one, or by two or more blended use.In this case, the blending amount of each resin is not hindering the blending amount being set as meeting target in the scope of the necessary physical property such as gas permeability.
In addition, in addition to the foregoing, also can use the known additives such as antioxidant, light stabilizer, lubricant, antistatic agent, and be set as the addition meeting target in the scope not hindering the necessary physical property such as electrical characteristics, mechanical property.
[manufacture method]
In the present embodiment, polyolefin-based porous film can be manufactured by dry process.The manufacture method using dry process is below described.
In the present embodiment, utilize the manufacture method of dry process to comprise the reel molding procedure of (A) shaping atresia reel, (B) is by the MD cold stretch operation of atresia reel along MD cold stretch.
Except these operations, more than one the operation be selected from group that the heat-setting procedure of the film heat setting through TD cold stretch operation forms along the TD cold stretch operation of TD cold stretch, (H) along the MD heat-setting procedure of MD heat setting, (D) along the MD heat drawing process of MD direction hot-stretch, (G) by the annealing in process operation, (C) that atresia reel are annealed by (F) by film by film by film can also be had.
In addition, in the present embodiment, can have that (I) implements surface-treated surface treatment procedure to film, (J) be coated with the painting process of other layers such as refractory layer on perforated membrane.
Wherein, MD refers to and extrudes direction when reel being extruded in (A) reel molding procedure, and TD refers to the direction perpendicular to MD.
((A) reel molding procedure)
Do not limit by method shaping for polyolefin resin composite, such as, by by polyolefine resin composition melting mixing in singe screw or the double screw extruder etc., with T-shaped die head or the first-class film extruding molten condition of circular die, with tractions such as casting roller (castroll) or carry-over pinch rolls, thus be shaped to reel.Now, it is desirable that use squeegee, aerator etc. the resin combination quenching of melt stage to be solidified.Thus, can want overstating for pore-forming platelet rule and arrange densely.
In addition, to draw ratio ((hauling speed of casting roller)/(by density conversion from die lip resin flow velocity out)) the not restriction during molten resin composition flowed out from die head with roller drawing-off, such as, from the viewpoint of gas permeability, mouldability, 10 ~ 600 times can be set as, be more preferably 20 ~ 500 times, more preferably 30 ~ 400 times.When draw ratio is more than 10 times, the perforated membrane of gas permeability excellence can be obtained, when draw ratio is below 600 times, easily stably draw the molten resin flowed out from die head.
In addition, draw ratio is set as 50 ~ 600 times, preferably the scope of 150 ~ 600 times time, can the birefringence of gained atresia reel be set in aftermentioned preferred scope, the birefringence of the perforated membrane of stretching perforate can be set in 2.0 × 10 thus -2~ 4.0 × 10 -2scope in.But, due to draw ratio and birefringence relation by the resin contained in resin combination kind, flow out from T-shaped die head time the impact of tensile viscosity etc., therefore, above-mentioned draw ratio is a benchmark only, finally preferably, repetition test etc. is carried out, then by draw ratio optimization in the birefringence limit that limit measures gained atresia reel.
In the present embodiment, the birefringence of the atresia reel obtained in (A) operation is preferably 3.0 × 10 -2above, 3.0 × 10 are more preferably -2~ 4.5 × 10 -2, be also more preferably 3.1 × 10 -2~ 4.0 × 10 -2, more preferably 3.2 × 10 -2~ 3.8 × 10 -2.The birefringence of atresia reel is 3.0 × 10 -2time above, thus obtained perforated membrane forms the tight pore structure of small-bore, obtains the effect improving proof voltage.As a result, the balance of resistance and proof voltage can be improved.In addition, if having 4.5 × 10 -2the atresia reel of the birefringence of following left and right, can improve the draw ratio flowed out by T-shaped die head like that and manufacture, and therefore, draws resin when atresia reel is shaping Absorbable organic halogens.
In the present embodiment, birefringence refers to MD refractive index and the TD specific refractivity (MD-TD) of the light of the wavelength relative to wavelength 590nm.
Birefringence is the anisotropic index representing object, when crystalline resin, its birefringence is the intrinsic birefringence of the crystal structure (platelet) being derived from crystal phase and is derived from the summation of both birefringences of molecularly oriented of amorphous phase.The birefringence of the atresia reel of present embodiment is also by the impact of both birefringences, crystal mutually in, along with the increase of draw ratio, the arrangement of platelet increases from unordered to systematicness, thus the eigenvalue that the value of birefringence has close to its crystal structure (platelet).In addition, in amorphous phase, due to the increase along with draw ratio, the molecularly oriented of MD increases, and thus the value of birefringence increases pro rata with this orientation, but when orientation is too high, causes rupturing.Therefore, the scope of above-mentioned birefringence is preferably set to and does not reach 4.5 × 10 of fracture -2following left and right.
It is generally acknowledged that resistance and proof voltage exist the anti-relation of the back of the body, such as, by improving any one stretching ratio such as MD cold stretch multiplying power, MD hot-stretch multiplying power, TD cold stretch multiplying power further, the aperture of gained perforated membrane becomes large, resistance can be reduced, cause the performance of proof voltage to reduce but then, thus be difficult to make both high balance.But, by by atresia reel to make its birefringence for 3.0 × 10 -2above and make latter openings surface area be that the mode of particular range is shaping, thus obtained perforated membrane because defining finer and close pore structure, so proof voltage improves.The balance of resistance and the proof voltage in the past can not reached can be realized thus.
In the present embodiment, atresia reel and the perforated membrane its stretching perforate obtained can be individual layers, also can have the sandwich construction obtained by different polyolefin resin composite laminated multi-layer.But, in this case, when forming the glass transition temperature of the polyolefin resin composite of each layer, fusing point difference, as Tg, Tm, adopt following value.
Glass transition temperature Tg: the peak of the Tg obtained when using the polyolefin resin composite forming each layer make monofilm and measure Tg.
Fusing point Tm: the minimum of the Tm obtained when using the polyolefin resin composite forming each layer make monofilm and measure Tm.
((F) annealing in process operation)
In the present embodiment, before by the operation ((B) operation) of atresia reel MD cold stretch, preferably annealing in process is carried out.In annealing in process operation, by implementing annealing in process to atresia reel, the degree of crystallinity of atresia reel can be improved, the perforated membrane that gas permeability, resistance are more excellent can be obtained.In addition, when improving the temperature of annealing in process, can improve the degree of crystallinity of atresia reel, can obtain the perforated membrane of gas permeability, resistance excellence, therefore, annealing in process is preferably at high temperature carried out, but excessive heat treatment will cause the melting of resin, become the reason of fault.Therefore, the temperature range of annealing in process is preferably (Tm-3 DEG C) ~ (Tm-30 DEG C), is more preferably (Tm-5 DEG C) ~ (Tm-20 DEG C).Tm represents the fusing point (DEG C) of the atresia reel before annealing in process.
In addition, annealing in process can be continuation mode, also can be intermittent mode.When carrying out annealing in process continuously, from effective viewpoint playing the effect of annealing in process, the processing time is preferably more than 0.5 minute, is more preferably more than 1 minute, more preferably more than 2 minutes.In addition, when carrying out annealing in process with intermittent mode, specifically, atresia reel is wound to implement annealing in process under the state on roller time, the processing time preferably according to batch time diameter suitably change.When determining the annealing in process time, preferably, such as, for skin and the internal layer (core side) of the atresia reel of batching, change the processing time, measure the key properties such as air permeability, the value of the skin and internal layer of obtaining atresia reel does not have the differentiated processing time.
((B) MD cold stretch operation)
In the present embodiment, along MD, cold stretch is implemented for atresia reel (being through the atresia reel after annealing in process operation when implementing annealing in process), makes atresia reel form crackle, thus can porous be realized.This cold stretch preferably uses multiple roller.Stretching ratio is now preferably 1.05 ~ 3.0 times, is more preferably 1.1 ~ 2.5 times, more preferably 1.2 ~ 2.0 times.By MD cold stretch multiplying power is set within the scope of this, can the birefringence of gained perforated membrane, aperture surface area etc. be controlled in suitable scope, the perforated membrane of the balancing good of resistance and proof voltage and mechanical strength can be obtained.In addition, when MD cold stretch multiplying power being set within the scope of this, gas permeability, the outward appearance (pinprick etc.) of perforated membrane are improved, and the stability of stretching also becomes good.
Wherein, in the present embodiment, MD stretching ratio (doubly) is obtained by following formula.
MD cold stretch multiplying power (doubly)=V 2/ V 1
Wherein, in above formula, V 1represent the roller speed (m/ minute) before cold stretch, V 2represent the roller speed (m/ minute) at the end of cold stretch.
Draft temperature in MD cold stretch operation preferably-20 DEG C ~ (Tm-30 DEG C), be more preferably-20 DEG C ~ (Tm-50 DEG C), also be more preferably 0 DEG C ~ (Tm-50 DEG C), more preferably 0 DEG C ~ (Tm-60 DEG C), be particularly preferably 10 DEG C ~ (Tm-70 DEG C).Because this draft temperature is more than-20 DEG C, effectively can prevent the fracture of film, due to for (Tm-30 DEG C) below, the perforated membrane that gas permeability, resistance are more excellent can be obtained.
When using multiple roller to implement MD cold stretch, draw speed between roller is (when under different stretch speed, multistage stretches, get the mean value of the draw speed between each roller) be preferably 20 ~ 10000%/minute, be more preferably 50 ~ 5000%/minute, more preferably 80 ~ 3000%/minute scope.Due to this draw speed be 20%/minute more than, further increase the productivity ratio of perforated membrane, and due to its be 10000%/minute below, the perforated membrane that gas permeability, resistance are more excellent can be obtained.It should be noted that, in embodiments, draw speed is obtained by following formula.
MD cold stretch speed (%/minute)=S 1/ { 2L 1/ (V 1+ V 2)
Wherein, S 1represent stretching ratio (%)=(V 2/ V 1-1) × 100, V 1represent the roller speed (m/ minute) before cold stretch, V 2represent the roller speed (m/ minute) after cold stretch, L 1represent the stretching distance (m) between roller.
((C) MD heat drawing process)
After MD cold stretch operation ((B) operation), by implementing hot-stretch for the cold stretch perforated membrane defining crackle along MD, can by the borehole enlargement in the MD direction of this crackle and immobilization.Therefore, in the present embodiment, preferably there is (C) MD heat drawing process.Stretching ratio is now preferably 1.5 ~ 3 times, is more preferably 1.8 ~ 2.8 times, more preferably 2.0 ~ 2.6 times.
By MD hot-stretch multiplying power is set as more than 1.5 times, can gas permeability be improved, by MD hot-stretch multiplying power is set as less than 3.0 times, the generation of pinprick and fracture etc. can be suppressed further.
It should be noted that, in the present embodiment, MD hot-stretch multiplying power (doubly) is obtained by following formula.
MD hot-stretch multiplying power (doubly)=V 4/ V 3
Wherein, in above formula, V 3represent the roller speed (m/ minute) before hot-stretch, V 4roller speed (m/ minute) after expression hot-stretch terminates.
In addition, the draft temperature in MD heat drawing process is preferably (Tm-40 DEG C) ~ (Tm-5 DEG C), is more preferably (Tm-35 DEG C) ~ (Tm-5 DEG C), more preferably (Tm-30 DEG C) ~ (Tm-5 DEG C).When this draft temperature is more than (Tm-40 DEG C), gas permeability becomes better.In addition, due to this draft temperature be (Tm-5 DEG C) below, the generation of pinprick, fracture and roller fusing etc. can be suppressed further.
In addition, when using multiple roller to implement hot-stretch along MD, draw speed between roller is (when under different stretch speed, multistage stretches, get the mean value of the draw speed between each roller) be preferably 20 ~ 10000%/minute, be more preferably 50 ~ 5000%/minute, more preferably 80 ~ 3000%/minute scope.Same with MD cold stretch, due to draw speed be 20%/minute more than, further increase the productivity ratio of perforated membrane, and due to its be 10000%/minute below, the perforated membrane that gas permeability, resistance are more excellent can be obtained.
It should be noted that, in embodiments, draw speed is obtained by following formula.
MD hot-stretch speed (%/minute)=S 2/ { 2L 2/ (V 3+ V 4)
Wherein, S 2represent MD hot-stretch multiplying power (%)=(V 4/ V 3-1) × 100, V 3represent the roller speed (m/ minute) before hot-stretch, V 4represent the roller speed (m/ minute) after hot-stretch, L 2represent the stretching distance (m) between roller.
((G) MD heat-setting procedure)
In the present embodiment, in order to lower MD thermal contraction, reduce when taking following (D) TD cold stretch operation crimping (bowing) phenomenon (distortion occurred during stretching) etc. that occurs in stenter, it is desirable to, there is following MD heat-setting procedure: at the temperature more than the draft temperature of MD heat drawing process, when substantially not stretching, heat treated being carried out to the film after MD heat drawing process, implementing heat setting.In this MD heat-setting procedure, from suppression perforated membrane to the viewpoint of MD thermal contraction, effectively, using multiple roller, speed difference is set between which, not occurring in the scope of the open defects such as fold, making film along MD lax (contraction).
((D) TD cold stretch operation)
In the present embodiment, TD cold stretch operation is preferably comprised further.Especially, for the film through (C) MD heat drawing process, use the stretchers such as stenter to implement to stretch along TD.Specifically, only TD cold stretch is carried out to the film through above-mentioned each operation (A), (F), (B), (C), (G).By stretching along TD, homogeneous TD can be obtained and stretch, and the borehole enlargement of the TD of film, compared with the perforated membrane obtained by longitudinal (MD) uniaxial tension, can average pore size be expanded.As a result, can give the gas permeability of perforated membrane excellence, resistance, and compared with longitudinal monadic stretching membrane with identical gas permeability, can obtain the film piercing through excellent strength, and can realize speedup from the viewpoint of productivity ratio, be therefore preferred.
When implementing, such as, single shaft tenter apparatus etc. is used to stretch along TD.
Stretching ratio along TD in TD cold stretch operation is preferably 1.05 ~ 2.0 times, is more preferably more than 1.10 ~ 1.5 times, more preferably 1.15 ~ 1.3 times.By this stretching ratio is set as more than 1.05 times, the gas permeability of perforated membrane becomes better, and by setting it to less than 2.0 times, film rupture when TD stretches is less likely to occur, TD stretches inequality.
In addition, by this stretching ratio is set in above-mentioned scope, can the birefringence of gained perforated membrane, aperture surface area etc. be controlled in suitable scope, the perforated membrane of the balancing good of resistance and proof voltage and mechanical strength can be obtained.
In addition, draft temperature T when stretching along TD 1(DEG C) is preferably (Tg+20)≤T 1, be more preferably (Tg+30)≤T 1, more preferably (Tg+40)≤T 1.In addition, preferred T 1≤ (Tm-20), is more preferably T 1≤ (Tm-30), more preferably T 1≤ (Tm-40).Wherein, Tg represents the glass transition temperature (DEG C) of the perforated membrane as TD cold stretch object.
About the stretching of resin molding, it is known that, draft temperature is higher, and stress is more not easy in film residual, and the dimensional stability of gained film is higher, therefore, implement in general high-temperature area near fusing point, when the atresia reel MD formed by polyolefin resin composite being stretched and carries out TD stretching after porous, surprisingly, when draft temperature being set as the value lower than common draft temperature described above, distinguish the perforated membrane that can obtain dimensional stability and improve.Find this phenomenon (effect) especially at film by particularly remarkable when being formed using polyethylene as the polyolefine resin composition of principal component.
In addition, obtain in the process of atresia reel, when carrying out TD stretching to the film height-oriented with high draw ratio near melting temperature, the strand network on the TD direction in resin lacks, and becomes the reason causing the stretch problems such as inequality, fracture due to local flow.Therefore, from this viewpoint, in order to homogeneous and stably carry out TD stretching, importantly, implement TD under the condition of stress that the molecular network on TD direction can produce when fully tolerant T D stretches to stretch.In the preferred range of above-mentioned TD cold stretch, polyolefin-based resins is the rubbery state that can be out of shape because of stretching, and has the winding density of the strand of the stress produced when being enough to abundant resistance to Tensile, thus can be homogeneous and stably stretch along TD.
In addition, when the polyolefin-based porous film based on polypropylene, as mentioned above, by implementing this operation in the scope that molecular network becomes fine and close temperature and TD cold drawing temperature of the present invention, TD can be suppressed to stretch uneven, Absorbable organic halogens ground manufactures the homogeneity biaxial stretch-formed perforated membrane higher than prior art.
In the present embodiment, the speed implemented when stretching along TD does not affect especially on gas permeability, resistance, from the viewpoint paying attention to productivity ratio, preferably comparatively fast.But, when draw speed is too fast, film fracture may be there is near stenter cloth gripper (tenterclip).Therefore, draw speed is preferably 10 ~ 5000%/minute, be more preferably 50 ~ 4000%/minute, more preferably 100 ~ 3000%/minute.
It should be noted that, TD cold stretch speed in present embodiment (%/minute) obtained by following formula.
TD cold stretch speed (%/minute)=V 3× ((W 2/ W 1)-1) × 100/L 2
Wherein, in above formula, W 2represent TD distance between bench marks length (unit: m), W after TD cold stretch in TD cold stretch operation 1represent TD distance between bench marks length (unit: m), V before TD cold stretch in TD cold stretch operation 3represent stenter linear velocity (unit: m/ minute), L 2represent TD cold stretch zone distance (unit m).
((H) heat-setting procedure)
In the present embodiment, in order to suppress the thermal contraction of TD, it is desirable that preferably have following heat-setting procedure: carry out heat treated when substantially not stretching for the film through (D) TD cold stretch operation and to TD heat setting.It should be noted that, here, in fact not only TD is by heat setting, and MD is also by heat setting.
From the view point of suppression TD thermal contraction and film fracture, heat-set temperature T now 2(DEG C) is preferably (Tm-40)≤T 2≤ (Tm-3), is more preferably (Tm-35)≤T 2≤ (Tm-3), is also more preferably (Tm-30)≤T 2≤ (Tm-3), more preferably (Tm-30) ~ (Tm-5).Wherein, Tm is the fusing point (DEG C) of atresia reel.In addition, use with polyethylene when being the polyolefine resin composition of principal component, preferably (Tm-15)≤T 2≤ (Tm-3).When use take polypropylene as the polyolefine resin composition of principal component, preferably (Tm-40)≤T 2≤ (Tm-20).
In addition, heat-set temperature T 2the draft temperature T of (DEG C) and (D) TD cold stretch operation 1the relation of (DEG C) is preferably T 2>=T 1, be more preferably T 2>T 1, be also more preferably T 2>=(T 1+ 1), more preferably T 2>=(T 1+ 5), T is particularly preferably 2>=(T 1+ 20), T most preferably is 2>=(T 1+ 50).Wherein, to T 2the upper limit be not particularly limited, preferred T 2≤ (T 1+ 150).
In this heat-setting procedure, can heat-treat, only implement heat setting to the film off-line batched, from the view point of the thermal contraction more effectively suppressing TD, be also feasible by film along the heat set relaxation of TD lax (contraction) while heat setting.
When implementing this heat setting in horizontal single shaft tenter apparatus, TD heat set relaxation can be carried out under the state held with stenter cloth gripper.
In addition, also configurable warm-up mill, by carrying out heat setting on this roller.In this case, can implement with a roller, also by configuring multiple roller, utilize the speed difference between roller and roller spacing, carrying out MD and TD heat set relaxation.In addition, large-scale drying oven also can be used to carry out heat setting.
Wherein, in heat-setting procedure, TD relaxation rate when carrying out heat set relaxation is obtained by following formula.
TD relaxation rate (%)=W 3/ W 2× 100
Wherein, in above formula, W 2represent TD distance between bench marks length (unit: m), the W after TD cold stretch 3represent the TD distance between bench marks length (unit: m) after heat setting.
((I) surface treatment)
In the present embodiment, in order to improve the compatibility etc. of perforated membrane and smears or solvent, also can use the known technologies such as Corona discharge Treatment machine, plasma processor, ozone treatment machine, flame processing machine, preferably hydrophilicity-imparting treatment be implemented to the film through (H) heat-setting procedure.
((J) is coated with)
In the present embodiment, at least one of the perforated membrane after also preferably can stating hydrophilicity-imparting treatment on the implementation implements coating on the surface.
Such as, can the heat-resisting porous layer be made up of inorganic filler (particulate) and binding agent be set on of a perforated membrane surface.In this case, binding agent in order to by between inorganic filler, the object that bonds of the surface of inorganic filler and porous layer and using.
In addition, when forming heat-resisting porous layer, known technology can be used.Such as, can form heat-resisting porous layer by method disclosed in Japanese Unexamined Patent Publication 2011-832 publication, thus obtained heat-resisting perforated membrane has excellent thermal endurance, can improve fail safe, the reliability of secondary cell further.
By manufacture method described above, the polyolefin-based porous film of balance than existing known technology excellence of proof voltage and resistance can be produced.In addition, according to the present embodiment, if implement the stretching along TD, compared with the perforated membrane obtained with uniaxial tension, mechanical strength can be improved.As a result, the separator of the high-performance secondary cell requiring greater security and battery performance can be suitable as.
Be explained above adoptable manufacture method in the present embodiment, but the manufacture method of polyolefin-based porous film is not limited thereto.Such as, the order of each operation can be the order shown in Fig. 4.
[the various characteristics of polyolefin-based porous film]
(film width conservation rate)
In the present embodiment, gained polyolefin-based porous film be benchmark with the atresia reel before MD cold stretch film width conservation rate is preferably 90 ~ 150%, be more preferably 95 ~ 140%, more preferably 100 ~ 130%.Wherein, when film width conservation rate is more than 90%, gas permeability becomes good, when film width conservation rate is less than 120%, the problem that is uneven, film rupture that stretches is less likely to occur.It should be noted that, film width conservation rate is herein obtained by following formula.
Film width conservation rate (%)=W/W 0× 100
In above formula, W 0(unit: m), W represents the TD distance between bench marks length (unit: m) of gained polyolefin-based porous film to the TD distance between bench marks length of the atresia reel before expression MD cold stretch.
(thickness)
In the present embodiment, the thickness of polyolefin-based porous film is not particularly limited, as long as the thickness required by its purposes, is generally 5 ~ 50 μm, is more preferably 8 ~ 40 μm, more preferably 10 ~ 30 μm.
(air permeability)
In the present embodiment, the air permeability of polyolefin-based porous film is not particularly limited, consider the balance with various physical property, by the thickness of film be 20 μm of conversions (that is, air permeability × (actual (real) thickness (μm) of 20/ film) of actual measurement, be preferably 10 ~ 600 seconds/100cc, be more preferably 30 ~ 500 seconds/100cc, also be more preferably 50 ~ 500 seconds/100cc, more preferably 50 ~ 400 seconds/100cc, be particularly preferably 100 ~ 400 seconds/100cc.Air permeability is measured by the method recorded in following embodiment.
(porosity)
In the present embodiment, be not particularly limited the porosity of polyolefin-based porous film, consider and the balance of various physical property, porosity is preferably 40 ~ 80%, is more preferably 45 ~ 75%, and more preferably 50 ~ 70%.Porosity measures by the method recorded in following embodiment.
(resistance)
In the present embodiment, being not particularly limited the resistance of polyolefin-based porous film, considering the balance with proof voltage, is that (that is, resistance × (actual (real) thickness (μm) of 20/ film) of actual measurement is preferably 1.0 Ω cm in 20 μm of conversions by the thickness of film 2below, 0.5 Ω cm is more preferably 2below, more preferably 0.3 Ω cm 2below.Resistance is measured by the method recorded in following embodiment.
(proof voltage)
In the present embodiment, the resistance of polyolefin-based porous film is not particularly limited, consider the balance with resistance, be 20 μm by the thickness of film to convert (namely, proof voltage × (actual (real) thickness (μm) of 20/ film) of actual measurement, be preferably more than 1.2kV, being more preferably more than 1.5kV, can also be more than 1.8kV.Proof voltage is measured by the method recorded in following embodiment.
(very big aperture)
The very big aperture (mode diameter (modediameter)) of the polyolefin-based porous film of present embodiment affects resistance and proof voltage, is preferably 0.2 ~ 0.5 μm, is more preferably 0.25 ~ 0.45 μm, more preferably 0.3 ~ 0.4 μm.When very big aperture is more than 0.2 μm, can resistance be reduced, when very big aperture is below 0.5 μm, proof voltage can be brought up to realistic scale.In addition, very big aperture controls by stretching conditions such as MD cold stretch multiplying power, MD hot-stretch multiplying power, TD cold stretch multiplying powers.Wherein, very big aperture is measured by the method recorded in following embodiment.
(piercing through intensity)
In the present embodiment, the intensity that pierces through of polyolefin-based porous film is not particularly limited, as long as pierce through intensity required by its purposes, generally, if the value when thickness of conversion film forming is 20 μm (that is, actual measurement to pierce through intensity × (actual (real) thickness (μm) of 20/ film) be more than 2.0N, when being then used as the separator of battery, it is no problem to use, and is preferably more than 2.5N, more preferably more than 3.0N.Pierce through intensity to measure according to the method recorded in following embodiment.
According to the manufacture method of above-mentioned perforated membrane, the polyolefin-based porous film with the gas permeability higher than existing known technology can be obtained.Ion permeability can be improved thus.In addition, when carrying out heat setting carry out TD cold stretch at the temperature lower than common draft temperature after, at the temperature higher than TD cold drawing temperature, permeability can be obtained improve and the more excellent perforated membrane of dimensional stability, such as, during separator as the high lithium rechargeable battery of energy density, fail safe, reliability are also improved.
(aperture surface area)
In the present embodiment, the aperture surface area of polyolefin-based porous film affects resistance and proof voltage.
The aperture surface area of polyolefin-based porous film is preferably 42.0m 2/ below g, is more preferably 35.0 ~ 42.0m 2/ g, more preferably 36.0 ~ 41.5m 2/ g, is particularly preferably 37.0 ~ 41.0m 2/ g.
Aperture surface area is 35.0m 2during/more than g, the resistance of perforated membrane can be reduced.On the other hand, when obtaining the polyolefin-based porous film of proof voltage raising according to the present embodiment, when aperture surface area is excessive, proof voltage can reduce, and distinguishes the advantage not making full use of present embodiment.But, if be 42.0m 2/ below g, then can bring up to realistic scale by proof voltage.
The aperture surface area of perforated membrane can be controlled by stretching conditions such as the orientation of above-mentioned atresia reel, MD stretching ratio, TD stretching ratios.Wherein, aperture surface area measures according to the method recorded in following embodiment.
(birefringence)
In the present embodiment, except the aperture surface area of polyolefin-based porous film being set in except in above-mentioned scope, when birefringence is set as particular range, the perforated membrane of the balance excellence of resistance and proof voltage and mechanical strength can be formed.
The birefringence of polyolefin-based porous film can control by forming the kind (difficulty of orientation) of polymer (polyolefin-based resins), the condition such as draw ratio, MD stretching ratio, TD stretching ratio of reel molding procedure that contain in the polyolefin resin composite of perforated membrane, is preferably 2.0 × 10 -2~ 4.0 × 10 -2, be more preferably 2.3 × 10 -2~ 3.5 × 10 -2, more preferably 2.5 × 10 -2~ 3.0 × 10 -2.By birefringence is set as 2.0 × 10 -2above, proof voltage and mechanical strength become good, by birefringence is set as 4.0 × 10 -2below, the stability in the mouldability of atresia reel, longitudinal stretching operation becomes good.
(TD stretch inequality)
In the present embodiment, the stretching inequality of polyolefin-based porous film is not particularly limited, as long as the stretching required by its purposes is uneven, generally, owing to having impact to each physical property of film, thickness difference as the uneven index that stretches is preferably within 30%, is more preferably within 20%, more preferably within 10%.TD stretching is uneven to be measured according to the method recorded in following embodiment.
It should be noted that, in the present embodiment, polyolefin-based porous film can be individual layer as mentioned above, also can be multilayer.In addition, the polyolefin-based porous film of single or multiple lift can be used alone, also can other the layer such as stacked refractory layer, uses as multilayer porous film.
Be explained above for implementing mode of the present invention, but the invention is not restricted to above-mentioned present embodiment.
It should be noted that, about each measured value of above-mentioned parameter, unless otherwise defined, measure in the same manner as the assay method of following embodiment.
Embodiment
Below enumerate embodiment and comparative example to further illustrate present embodiment, but present embodiment only otherwise exceeding its main idea is not just limited by the following examples.Wherein, the assay method of various physical property is as described below with the method manufacturing perforated membrane.
(thickness)
The thickness of perforated membrane is according to JISK7130(1992) A-2 method dial gauge measures.
(glass transition temperature Tg)
The glass transition temperature Tg of atresia reel (before annealing in process) uses viscoplasticity spectrometer (ProductName " EXSTARDMS6100 " SIINanoTechnologyInc. system), in stretch mode (programming rate=2 DEG C/min, frequency=1Hz) under obtain the summit temperature of loss elastic modulus E ' ', it can be used as glass transition temperature Tg (DEG C).
(fusing point Tm)
Differential scanning calorimeter (ProductName " EXSTAR6000 ", SIINanoTechnologyInc. system) is used to measure the fusing point of atresia reel (before annealing in process).Measure with the summit temperature at melting peak during 10 DEG C/min of programming rate heating, as fusing point Tm(DEG C).
(air permeability)
About perforated membrane, Gurley air permeability meter (Toyo Seiki Inc.) is used to measure the airtight degree (airresistance) of perforated membrane according to JISP-8117.This measured value is scaled the thickness 20 μm of film, as air permeability.
(very big aperture, aperture surface area)
Use pore size distribution determinator (ProductName " Autopore9520 type ", Shimadzu Seisakusho Ltd.'s system), measure very big aperture (mode diameter) and aperture surface area by mercury injection method.
(resistance)
As electrolyte, by propylene carbonate and ethylene carbonate (volume ratio: 50/50) mix, under the state making it fully soak into sample, apply alternating voltage between electrode, mensuration resistance.This measured value is scaled the thickness 20 μm of film, as resistance.Judge to evaluate according to following benchmark.
More than 1.5 Ω cm 2: ×
1.5 Ω cm 2below: △
1.0 Ω cm 2below: zero
0.5 Ω cm 2below: ◎
(proof voltage)
With the aluminum electrode clamping perforated membrane of diameter 3cm, apply the load of 15g, the proof voltage analyzer (TOS9201) that itself and the industry of chrysanthemum aqueous electron manufacture is connected, implements to measure.Condition determination is with speed applying alternating voltage (60Hz) of 1.0kV/ second, measures magnitude of voltage during short circuit.By the thickness 20 μm of this measured value conversion film forming, as proof voltage.Judge to evaluate according to following benchmark.
More than 1.5kV: ◎
Below 1.5kV: zero
Below 1.0kV: △
Below 0.5kV: ×
(piercing through intensity)
Use the Portable compressed testing machine (ProductName " KES-G5 ") of KATOTECHCO., LTD., measure under the condition of the radius of curvature 0.5mm of needle tip, puncture speed=2mm/ second and pierce through intensity.This measured value is converted into film thickness 20 μm, as piercing through intensity.Judge to evaluate according to following benchmark.
More than 2.5N: ◎
Below 2.5N: zero
Below 2.0N: △
Below 1.5N: ×
(birefringence)
Use measuring difference of phases device (ProductName " KOBRA21-ADH ", prince measures machine (strain)), adopt mensuration wavelength 590nm to measure.Wherein, when measuring perforated membrane, by infiltrating the swab stick having silicone oil (dimethyl siloxane), porous film surface being coated with thin layer, measuring under the state be translucent.
(fusing and short circuit test)
Prepare 2 pieces of nickel foils 2A, 2B of thickness 10 μm, use " Teflon " (trade mark) adhesive tape on nickel foil 2B, carry out pasting the peristome 5 of the 10mm × 10mm formed as shown in Figure 1 in advance.The perforated membrane 1 making fully to be impregnated with the lithium tetrafluoroborate solution (solvent: propylene carbonate/ethylene carbonate/gamma-butyrolacton=1/1/2) that the 1mol/ as electrolyte rises is sealed on another nickel foil 2A, as shown in Figure 2, in the mode making perforated membrane 1 all cover the peristome 5 that nickel foil 2B is arranged, by superimposed to nickel foil 2A, 2B, then, clamp with commercially available glass plate 3A and 3B, make working sample.On the other hand, at the heating plate 9 of the below of the cylinder 14 of hydraulic type press 13 configuration diameter phi 60mm, mounting is provided with the wooden plate 6 of the thickness 8mm of thermocouple 7A and 7B thereon, then, load the silicane rubber plate 8 of the working sample shown in Fig. 2, thickness 6mm successively, be forced into 1MPa with hydraulic type press 13.By wire 12A with 12B, nickel foil 2A with 2B is connected with resistance measurement device (pacifying rattan electrically LCR instrument " AG-4311 " (trade mark) processed), connects thermocouple 7A and thermometer 16 in addition, under the condition exchanging 1V, 1kHz, measure temperature and resistance.Now, the wiring 11 of stretching out from heater 10 is connected with temperature controller 18 with thermocouple 7B, with the speed of 15 DEG C/min from room temperature to 200 DEG C.
In temperature-rise period, will 10 be reached 3temperature (temperature measured with thermocouple 7A) during Ω is denoted as fusion temperature, after this, by resistance value again lower than 10 3temperature (temperature measured with thermocouple 7A) during Ω is denoted as short circuit temperature.
(mean molecule quantity, molecular weight distribution)
Use following device, measure mean molecule quantity (Mw, Mn) and molecular weight distribution (Mw/Mn) according to following condition gel permeation chromatography (GPC).
GPC determinator: HLC-8121GPC/HT(TosohCorporation system)
Post: TSKgelGMH hR-HHT × 2 piece
Unit temp: complete trails 155 DEG C
Eluant, eluent: o-dichlorohenzene (0.05%BHT) 1ml/ minute
Sample size: 500 μ l(0.5mg/ml)
Detector: RI
Calibration curve: use mean molecule quantity and the known polystyrene of molecular weight distribution to make.
(TD stretch inequality)
Use the continuous thickness gauge of contact pin type ((strain) mountain message gas Inc., TOF-5R01), measure under the condition measuring spacing 1mm, 5 rolling averages.In addition, obtain thickness difference based on this result, according to following determinating reference, evaluate TD and stretch uneven.
Thickness difference (%)=((maximum of thickness)-(minimum value of thickness))/average thickness × 100
Less than ◎: 20%
Less than zero: 30%
Less than △: 40%
×: more than 40%
(TD dimensional stability)
For the MD monadic stretching membrane before TD cold stretch, a segment mark line is marked in advance on its TD direction, to the perforated membrane through TD cold stretch operation and heat-setting procedure, measure distance between bench marks length rapidly, then place 24 hours under the atmosphere temperature of 30 DEG C not hindering under the state of the contraction in TD direction, and then measurement distance between bench marks, obtain the size changing rate in film width TD direction.In addition, dimensional stability is evaluated according to following benchmark.
Less than ◎: 2%
Less than zero: 4%
Less than △: 6%
×: more than 6%
(film width conservation rate)
On its TD direction, a segment mark line is marked in advance to atresia reel, measures this distance between bench marks length W 0.In addition, to using the perforated membrane of this atresia reel manufacture again to measure distance between bench marks length W, film width conservation rate is obtained according to the following formula.
Film width conservation rate (%)=W/W 0× 100
In above formula, W 0(unit: m), W represents that gained polyolefin-based porous film (is W when uniaxial tension perforated membrane to the TD distance between bench marks length of expression atresia reel 1, be W when biaxial stretch-formed perforated membrane 3) TD distance between bench marks length (unit: m).
1. embodiment A
(polyolefin-based resins used in embodiment A 1 ~ 8 and Comparative examples A 1)
In embodiment A 1 ~ 8, Comparative examples A 1, as polyolefin resin composite, use following polyethylene.
(PE-A1): polyethylene and ethylene copolymers (comonomer type: propylene), SuntecHDS160S(Asahi Chemical Corp system), density=0.960g/cm 3, MI=0.8g/10 minute, weight average molecular weight=140,000, molecular weight distribution=5.3.
(PE-A2): polyethylene and ethylene copolymers (comonomer type: 1-butylene), NipolonHard#6300(TosohCorporation), density=0.962g/cm 3, MI=0.25g/10 minute, weight average molecular weight=180,000, molecular weight distribution=15.3.
(PE-A3): the blend composition of PE-A1/PE-A2=50 quality %/50 quality %, density (calculated value)=0.961g/cm 3, MI=0.43g/10 minute.
(PE-A4): Natene, SuntecHDB161(Asahi Chemical Corp system), density=0.963g/cm 3, MI=1.3g/10 minute, weight average molecular weight=150,000, molecular weight distribution=8.4.
(embodiment A 1)
By polyethylene single screw extrusion machine (L/D=32) melting mixing of above-mentioned PE-A1, extruded by T-shaped die head (clothes hanger type (coathanger)), while cool with squeegee, while draw with the draw ratio of 400 times with casting roller, the atresia reel of molding thickness 20 μm, is then wound to ((A) operation) on 3 inches of paper webs.Condition of molding is shown in Table A 1.After this, be wound under the state on paper web, in the drying machine of 120 DEG C, leaving standstill 3 hours, carry out annealing in process ((F) operation).
Then, in room temperature (rt) the atresia reel implementing annealing in process is carried out to the MD cold stretch ((B) operation) of 1.5 times, then, the MD hot-stretch ((C) operation) of 2.5 times is carried out at 120 DEG C, then at 125 DEG C, carry out MD heat setting ((G) operation) continuously, be that polyethylene (hereinafter referred to as " PE ") the uniaxial tension perforated membrane of the embodiment A 1 of 3.75 times is wound on 3 inches of paper webs by total for MD stretching ratio.This uniaxial tension condition and various evaluation result are shown in Table A 2.
(embodiment A 2 ~ 4)
Use polyethylene and ethylene copolymers PE-A2, obtain the atresia reel of thickness 26 μm with the draw ratio of 300 times, in the same manner as embodiment A 1, obtain the PE uniaxial tension perforated membrane of embodiment A 2.
In addition, embodiment A 3 is identical with embodiment A 1 except increase the roller speed (draw speed) of each operation compared to embodiment A 2 except with A4.These uniaxial tension conditions and various evaluation result are shown in Table A 2.
(embodiment A 5)
PE-A3(is dry mixed product) with melting mixing in the single screw extrusion machine with Dulmage screw rod, extruded by the T-shaped die head of 160 DEG C, obtain the atresia reel of thickness 28 μm with the draw ratio of 300 times, annealing in process condition is identical with embodiment A 3 with MD stretching condition.This uniaxial tension condition and various evaluation result are shown in Table A 2.
(Comparative examples A 1)
Use Natene PE-A4, extruded by the T-shaped die head of 200 DEG C, obtain the atresia reel of draw ratio 300 times, thickness 18 μm, obtain the PE uniaxial tension perforated membrane of Comparative examples A 1 in the same manner as embodiment A 1.This uniaxial tension condition and various evaluation result are shown in Table A 2.
As shown in Table A 2, the aperture surface area of Comparative examples A 1 has exceeded 42m 2/ g, birefringence also has lower than 2.0 × 10 -2value.
[stretching condition of biaxial stretch-formed perforated membrane and various physical property]
(embodiment A 6)
Use stenter ((strain) city's metal working industry Inc.), under temperature 60 C, the uniaxial tension perforated membrane obtained in embodiment A 5 is stretched 1.14 times along TD, at the temperature of 125 DEG C, edge TD carries out heat setting in lax 0.9% limit, obtains the biaxial stretch-formed perforated membrane of PE that the total stretching ratio of TD is 1.13 times.This TD stretching condition and various evaluation result are shown in Table A 3.
[manufacturing condition of heat-resisting multilayer porous film and various physical property]
(synthesis of acrylic ester latex)
In the same manner as the synthesis example 1 of Japanese Unexamined Patent Publication 2011-832 publication, preparation average grain diameter 90nm, containing (methyl) acrylate monomer, unsaturated carboxylic acid monomer and cross-linkable monomer as the latex 1 of the acrylate based copolymer of material unit.
(preparation of coating fluid)
Then, make 88.4 mass parts as inorganic particle with calcined kaolin 1(kaolinite (Al 2si 2o 5(OH) 4) for principal component, the material (average grain diameter 1.89 μm) that wet type kaolin high-temperature calcination process obtained and 11.6 mass parts are evenly dispersed in the water of 150 mass parts as the above-mentioned latex 1 of resinoid bond, prepare coating fluid 1.
(embodiment A 7,8)
Corona discharge Treatment is carried out to the surface of the longitudinal uniaxial tension perforated membrane of the PE used in embodiment A 5 and embodiment A 6 and the biaxial stretch-formed perforated membrane of PE, carries out hydrophilicity-imparting treatment (operation (I)).Use micro gravure coating machine applied coating solution 1 on these PE perforated membranes, at the temperature of 60 DEG C, carry out drying, embodiment A 7 and embodiment A 8 obtain and are formed by the heat-resisting perforated membrane of the heat-resisting porous layer of 7 μm (the binding agent ratio 5.0% in heat-resisting porous layer) on the surface of PE perforated membrane.Their various evaluation of physical property results are shown in Table 4.
Table A 1
Table A 2
Note 1) TD stretching ratio obtains as follows: the graticule TD direction of the perforated membrane before stenter stretches being arranged 5cm interval, and after stenter stretches, half-mark distance between centers of tracks is obtained.
Note 2) value after 20 μm of thickness conversions.
Table A 3
Note 1) be converted into the value of the thickness 20 μm of substrate layer.
Table A 4
As shown in Table A 2 and Table A 3, as embodiment A 1 ~ 5, the aperture surface area of perforated membrane is in 35.0 ~ 42.0m 2the scope of/g is interior and birefringence is in 2.0 × 10 -2~ 4 × 10 -2scope in time, resistance and proof voltage and the balance piercing through intensity are good.
In addition, as can be seen from the result of Table A 4, there is the heat-resisting perforated membrane of the heat-resisting porous layer employing inorganic filler in fusing and short circuit test, after 146 DEG C of lower opening obturations (fusing), even if also maintain molten state under the high temperature more than 200 DEG C, thermal endurance is still very excellent.
2. Embodiment B
In Embodiment B 1-6, comparative example B1 ~ 3, as polyolefine resin composition, use following polyethylene.
(PE-B1): SuntecHDS160S(Asahi Chemical Corp system), density=0.960g/cm 3, MI=0.8g/10 minute.
(PE-B2): NipolonHard#5110(TosohCorporation), density=0.961g/cm 3, MI=0.9g/10 minute.
(PE-B3): NipolonHard#6300(TosohCorporation), density=0.962g/cm 3, MI=0.25g/10 minute.
(PE-B4): the blend composition of PE-1/PE-3=50 quality %/50 quality %, density (calculated value)=0.961g/cm 3, MI=0.43g/10 minute.
(PE-B5): SuntecHDB161(Asahi Chemical Corp system), density=0.963g/cm 3, MI=1.3g/10 minute.
(PE-B6): SuntecHDS362(Asahi Chemical Corp system), density=0.952g/cm 3, MI=0.8g/10 minute.
(Embodiment B 1 ~ 3)
By the polyethylene of above-mentioned PE-B1 ~ 3 melting mixing in single screw extrusion machine, extrude from T-shaped die head (clothes hanger type), while cool with squeegee, while draw with casting roller, shaping atresia reel, is then wound to ((A) operation) on 3 inches of paper webs.Now, draw ratio is set as more than 300 times, makes the birefringence of atresia reel be 3.0 × 10 -2above.
After this, each atresia reel be wound on paper web is left standstill 3 hours in the drying machine of 120 DEG C, carries out annealing in process ((F) operation).
Then, in room temperature (rt) along MD, 1.5 times of cold stretch ((B) operation) are carried out to the atresia reel implementing annealing in process, then, carry out the hot-stretch ((C) operation) of 2.5 times along MD at 120 DEG C, then at 125 DEG C, carry out heat setting continuously, obtain polyethylene (hereinafter referred to as " PE ") the uniaxial tension perforated membrane that the total stretching ratio of MD is 3.75 times.The various evaluation results obtaining various condition till this perforated membrane and gained PE uniaxial tension perforated membrane are shown in table B1.
(Embodiment B 4)
Except improving MD draw speed (cold stretch, both hot-stretch), changing except the time of heat setting, under the condition identical with Embodiment B 3, obtain PE uniaxial tension perforated membrane.This uniaxial tension condition and various evaluation result are shown in table B1.
(Embodiment B 5)
Use PE-B4 as polyolefin-based resins, melting mixing in single screw extrusion machine (screw rod with Dulmage), extrudes from T-shaped die head, while cool with squeegee, while draw with casting roller, shaping atresia reel, is then wound to ((A) operation) on 3 inches of paper webs.Now, draw ratio is set as 300 times, the birefringence of atresia reel is 3.5 × 10 -2.Annealing conditions is identical with Embodiment B 1 with longitudinal uniaxial tension condition.The various evaluation results obtaining various condition till this perforated membrane and gained PE uniaxial tension perforated membrane are shown in table B1.
(comparative example B1)
Use PE-B5 as polyolefine resin composition, obtain the atresia reel that draw ratio is 188 times, under the MD stretching condition identical with Embodiment B 1, obtain PE uniaxial tension perforated membrane.By the birefringence of the atresia reel before the annealing in process of shaping acquisition lower than 3.0 × 10 -2(2.0 × 10 -2).The various evaluation results obtaining various condition till this perforated membrane and gained PE uniaxial tension perforated membrane are shown in table B1.
(comparative example B2)
Use PE-B5 as polyolefine resin composition, obtain the atresia reel that draw ratio is 300 times, under the MD stretching condition identical with Embodiment B 1, obtain PE uniaxial tension perforated membrane.Be 3.0 × 10 by the birefringence of the atresia reel before the annealing in process of shaping acquisition -2above (3.1 × 10 -2), aperture surface area is more than 42.0m 2/ g.The various evaluation results obtaining various condition till this perforated membrane and gained PE uniaxial tension perforated membrane are shown in table B1.
(comparative example B3)
As polyolefine resin composition, use density is 0.952g/cm 3pE-B6, shown in molding condition setting Cheng Rubiao B1, in addition, under the condition identical with Embodiment B 1, obtain PE uniaxial tension perforated membrane.By the birefringence of the atresia reel before the annealing in process of shaping acquisition lower than 3.0 × 10 -2(2.9 × 10 -2).The various evaluation results obtaining various condition till this perforated membrane and gained PE uniaxial tension perforated membrane are shown in table B1.Wherein, the density of comparative example B3 is lower than 0.958, and perforate is insufficient.Therefore, judge that the physical property beyond gas permeability is unworthy evaluating and stopping.
[stretching condition of biaxial stretch-formed perforated membrane and various physical property]
(Embodiment B 6)
Use the stenter ((strain) city's metal working industry Inc.) of off-line, under temperature 60 C, the uniaxial tension perforated membrane obtained under the condition of Embodiment B 5 is stretched 1.14 times along TD, then carry out heat setting, thus obtain the biaxial stretch-formed perforated membrane of PE.Stretching condition till this TD stretching condition and various evaluation result are shown in table B2.
Note 1) measured value before annealing in process.
Note 2) stretching ratio: cold stretch multiplying power be with cold stretch before the value obtained for benchmark of roller speed, hot-stretch multiplying power be with cold stretch after the value obtained for benchmark of roller speed.
Note 3) value after 20 μm of thickness conversions.
Note 4) due to the non-constant of gas permeability, therefore judge to be not suitable as separator and undetermined.
Note 5) export the roller speed before representing MD cold stretch, batch the roller speed after representing MD heat setting.
Table B1
Note 1) measured value when not having an annealing in process.
Note 2) value after 20 μm of thickness conversions.
Table B2
As shown shown in B1 and B2, the polyolefin-based porous film of embodiment and the birefringence of atresia reel are lower than 3.0 × 10 -2perforated membrane (comparative example B1, B3) or aperture surface area more than 42.0m 2the perforated membrane (comparative example B2) of/g is compared, and has excellent resistance and proof voltage and the balance piercing through intensity.In addition, density is used to be less than the comparative example B3(0.952g/cm of the vistanex of 0.960 3) gas permeability extreme difference, be unworthy evaluate.
3. Embodiment C
(polyethylene-based longitudinal uniaxial tension perforated membrane PE-C1)
As polyolefin-based resins, use MI=0.2g/10 minute, density=0.963g/cm 3, with GPC measure weight average molecular weight (Mw)=210,000, molecular weight distribution (Mw/Mn)=16 Natene.With single screw extrusion machine by the melting under the design temperature of 210 DEG C of this resin, extrude from the T-shaped die heads of 210 DEG C (die lip gap=9mm).While this molten resin is cooled with squeegee, while with being set as that the casting roller of 110 DEG C draws.Draw ratio is now 300 times, obtains the atresia reel that thickness is 27 μm.
Then, this atresia reel is implemented continuously to the heat treatment of 3 minutes in the annealing furnace of 120 DEG C, then, adopt 1 section, the 1.5 times cold stretch (room temperature) implemented along MD, then 3 sections (waiting draw speed (%/minute)), 2.5 times of hot-stretch (120 DEG C) implemented along MD are adopted, then at the temperature of 125 DEG C, only implement the heat setting to MD further, obtain polyethylene-based longitudinal uniaxial tension perforated membrane PE-C1 that thickness is 24 μm.Wherein, the manufacturing condition of atresia reel, longitudinal uniaxial tension perforated membrane and their various characteristic values are as shown in table C1.
(polypropylene-based longitudinal uniaxial tension perforated membrane PP-C1)
As polyolefin-based resins, use isotactic homo-polypropylene (MI=0.5g/10 minute, the density=0.910g/cm of ProductName " PrimePolyproE111G " 3, PrimePolymerCo., Ltd. system).With single screw extrusion machine by the melting under the design temperature of 260 DEG C of this polypropylene-based resin, extrude from the T-shaped die heads of 240 DEG C (die lip gap=2.5mm).While this molten resin is cooled with squeegee, while with being set as that the casting roller of 130 DEG C draws.Draw ratio is now 100 times, obtains the atresia reel that thickness is 28 μm.
Then, this atresia reel is implemented continuously to the heat treatment of 15 minutes in the annealing furnace of 140 DEG C, then, adopt 1 section, the 1.1 times cold stretch (room temperature) implemented along MD, then 3 sections (waiting draw speed (%/minute)), 2.7 times of hot-stretch (130 DEG C) implemented along MD are adopted, then implement the heat setting to MD further, obtain polypropylene-based longitudinal uniaxial tension perforated membrane PP-C1 that thickness is 24 μm.Wherein, the manufacturing condition of atresia reel, longitudinal uniaxial tension perforated membrane and their various characteristic values are as shown in table C1.
(Embodiment C 1)
Stenter (metal working industry Inc. of city) is used PE uniaxial tension perforated membrane PE-C1 to be carried out to the TD cold stretch of 1.1 times at the temperature of 25 DEG C, then in heat-setting procedure, carry out heat setting with under the state at the two ends of stenter cloth gripper holding film at the temperature of 125 DEG C, obtaining polyethylene (hereinafter referred to as PE) is biaxial stretch-formed perforated membrane.The wind speed of each operation now is all set to 9.3m/ second.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(Embodiment C 2)
Except being set as except 70 DEG C by TD cold drawing temperature, under the condition identical with Embodiment C 1, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(Embodiment C 3)
Except being set as except 1.2 times by TD cold stretch multiplying power, under the condition identical with Embodiment C 1, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(Embodiment C 4)
Except being set as except 70 DEG C by TD cold drawing temperature, under the condition identical with Embodiment C 3, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(Embodiment C 5)
Except being set as except 100 DEG C by TD cold drawing temperature, under the condition identical with Embodiment C 3, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(Embodiment C 6)
Except heat-set temperature being set as except 120 DEG C, under the condition identical with Embodiment C 3, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(Embodiment C 7)
Except heat-set temperature being set as except 120 DEG C, under the condition identical with Embodiment C 4, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(Embodiment C 8)
Except heat-set temperature being set as except 120 DEG C, under the condition identical with Embodiment C 5, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(Embodiment C 9)
Except heat-set temperature being set as except 110 DEG C, under the condition identical with Embodiment C 4, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(comparative example C1)
Using the film of PE-C1 as comparative example C1.The result of various evaluation is shown in table C2.
(comparative example C2)
Use PE longitudinal uniaxial tension perforated membrane PE-C1, at the temperature of 70 DEG C, carry out the TD cold stretch of 1.2 times in TD cold stretch operation, then in heat-setting procedure, at identical with TD cold drawing temperature 70 DEG C, implement heat setting, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(comparative example C3)
Except heat-set temperature being set as except 90 DEG C, under the condition identical with comparative example C2, obtain PE system biaxially-stretched film.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.
(comparative example C4)
Except heat-set temperature being set as except 130 DEG C, under the condition identical with comparative example C2, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C2.Under this condition, owing to there is film rupture in TD cold stretch way, so there is no the film that obtaining value must be evaluated.
(comparative example C5)
Except being set as except 110 DEG C by TD cold drawing temperature and heat-set temperature, under the condition identical with comparative example C2, obtain the biaxial stretch-formed perforated membrane of PE system.The condition of TD cold stretch and TD heat setting and the result of various evaluation are shown in table C2.Under this condition, owing to there is film rupture in TD cold stretch way, so there is no the film that obtaining value must be evaluated.
(Embodiment C 10)
Stenter (metal working industry Inc. of city) is used PP uniaxial tension perforated membrane PP-C1 to be carried out to the TD cold stretch of 1.2 times at the temperature of 28 DEG C, then in heat-setting procedure, carry out heat setting with under the state at the two ends of stenter cloth gripper holding film at the temperature of 140 DEG C, obtaining polypropylene (hereinafter referred to as PP) is biaxial stretch-formed perforated membrane.The wind speed of each operation now is all set to 13.7m/ second.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C3.
(Embodiment C 11)
Except TD cold drawing temperature being set as 70 DEG C, wind speed is set as 18.2m/ second except, under the condition identical with Embodiment C 10, obtain the biaxial stretch-formed perforated membrane of PP system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C3.
(Embodiment C 12)
Except TD cold drawing temperature being set as 100 DEG C, wind speed is set as 18.2m/ second except, under the condition identical with Embodiment C 10, obtain the biaxial stretch-formed perforated membrane of PP system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C3.
(Embodiment C 13)
Except heat-set temperature being set as except 130 DEG C, under the condition identical with Embodiment C 10, obtain the biaxial stretch-formed perforated membrane of PP system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C3.
(Embodiment C 14)
Except heat-set temperature being set as except 130 DEG C, under the condition identical with Embodiment C 11, obtain the biaxial stretch-formed perforated membrane of PP system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C3.
(Embodiment C 15)
Except heat-set temperature being set as except 130 DEG C, under the condition identical with Embodiment C 12, obtain the biaxial stretch-formed perforated membrane of PP system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C3.
(Embodiment C 16)
Except TD cold drawing temperature being set as 126 DEG C, being set as except 146 DEG C by heat-set temperature, under the condition identical with Embodiment C 11, obtain the biaxial stretch-formed perforated membrane of PP system.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C3.
(comparative example C6)
Using the film of PP-C1 as comparative example C6.The result of various evaluation is shown in table C3.
(comparative example C7)
Use PP-C1, at the temperature of 140 DEG C, carry out the TD cold stretch of 1.2 times, then in heat-setting procedure, at identical with TD cold drawing temperature 140 DEG C, implement heat setting, obtain the biaxial stretch-formed perforated membrane of PP system.The wind speed of each operation is now set to 18.2m/ second.The condition of TD cold stretch and heat setting and the result of various evaluation are shown in table C3.
The manufacture method of folded longitudinal uniaxial tension perforated membrane (three layer by layer)
Isotactic homo-polypropylene single screw extrusion machine melting under the design temperature of 260 DEG C of the ProductName " PrimePolyproE111G " used by above-mentioned PP-C1, extrudes from the T-shaped die heads of 260 DEG C (die lip gap=1mm).While this molten resin is cooled with squeegee, while with being set as that the casting roller of 130 DEG C draws.The draw ratio obtained now is the atresia reel PP-C2 of 90 times.
In addition, ProductName " SuntecHDB161 " (MI=1.3g/10 minute, density=0.963g/cm is used 3, Asahi Chemical Corp's system) Natene, in single screw extrusion machine, under the design temperature of 180 DEG C, make it melting, extrude from the T-shaped die heads of 180 DEG C (die lip gap=2.5mm).While this molten resin is cooled with squeegee, while with being set as that the casting roller of 100 DEG C draws.Draw ratio is now set to 350 times.The manufacturing condition of above-mentioned atresia reel PP-C2, PE-C2 and various characteristic value are as shown in table C4.
Then, be PE-C2 to make internal layer, the two skins mode that is PP-C2, be installed on the efferent of 3 axles, with the output speed of 8m/ minute, by the pressure thermo-compressed of 2.7kg/cm between the warm-up mill of temperature 132 DEG C, batch the atresia reel with 3 multilayer laminated structure.
Then, press reel at the temperature of 130 DEG C, carry out continuous annealing process in 30 minutes layer by layer to 3, further in MD cold stretch operation, carry out 1.3 times (room temperature) to stretch, in MD heat drawing process, carry out 2.5 times (120 DEG C) to stretch, in MD heat-setting procedure, at the temperature of 130 DEG C, carry out the MD heat set relaxation of 10%, stacked uniaxial tension perforated membrane (PP-C2/PE-C2/PP-C2) is batched.Longitudinal uniaxial tension condition of this stacked uniaxial tension porous layer and characteristic value thereof are as shown in table C5.
(Embodiment C 17)
Use the stacked longitudinal uniaxial tension perforated membrane be made up of above-mentioned 3 layers (PP-C2/PE-C2/PP-C2), carry out the cold stretch of 1.2 times along TD at the temperature of 100 DEG C, then, in heat-setting procedure, at the temperature of 130 DEG C, carry out heat setting, obtain the laminated biaxially-stretched perforated membrane of Embodiment C 17.The stretching condition of this biaxial stretch-formed perforated membrane and the result of various evaluation are shown in table C6.
(comparative example C8)
Using above-mentioned stacked longitudinal uniaxial tension perforated membrane as comparative example C8.The result of its various evaluation is shown in table C6.
(comparative example C9)
Above-mentioned stacked longitudinal uniaxial tension perforated membrane is carried out at the temperature of 100 DEG C the stretching of 1.2 times along TD, then, in heat-setting procedure, at the temperature of identical with TD cold drawing temperature 100 DEG C, carry out heat setting, obtain laminated biaxially-stretched perforated membrane.The condition of this biaxial stretch-formed perforated membrane and the result of various evaluation are shown in table C6.
(comparative example C10)
Except being set as except 126 DEG C by TD cold drawing temperature and heat-set temperature, under the condition identical with comparative example C9, obtain laminated biaxially-stretched perforated membrane.The condition of this biaxial stretch-formed perforated membrane and the result of various evaluation are shown in table C6.
(Embodiment C 18)
Corona discharge Treatment is implemented to the biaxial stretch-formed perforated membrane of the PE obtained under the condition of Embodiment C 4, with the coating fluid 1 modulated in micro gravure coating machine coating Examples A, then at the temperature of 60 DEG C, carry out drying, obtain the heat-resisting perforated membrane (Embodiment C 18) of the heat-resisting porous layer (the binding agent ratio in heat-resisting porous layer is 5.0%) with 7 μm.As shown shown in C7, this multilayer porous film is relative to before coating (Embodiment C 4), and the reduction of gas permeability is slight.
[table C1]
[table C2]
[table C3]
Project Unit PE-C2 PP-C2
Extrusion temperature ℃ 180 260
Die head temperature ℃ 180 260
Die lip gap mm 2.5 1
Draw ratio Doubly 350 90
Fusing point (Tm) ℃ 132 166
[table C4]
[table C5]
Note 1) 20 μm of thickness conversion values.
[table C6]
Note 1) Jiang Ji village layer thickness is the value (ignoring the thickness of heat-resisting porous layer) after basis conversion with 20 μm
[table C7]
As can be seen from the result shown in table C2, table C3 and table C6, as the manufacture method of polyolefin-based porous film, carry out heat setting at the temperature higher than TD draft temperature after, by carrying out heat setting in the condition and range of Tm-40 DEG C ~ Tm-3 DEG C, gained perforated membrane maintains good dimensional stability, and can obtain the more much higher pore membrane of gas permeability.
utilizability in industry
The polyolefin-based porous film obtained by the present invention especially can compatibly for the separator of high-performance secondary cell.
description of reference numerals
The perforated membrane of 1 infiltration electrolyte
2A nickel foil
2B nickel foil
3A glass plate
3B glass plate
4Teflon(trade mark) adhesive tape
5 peristomes
6 wooden plates
7A thermocouple
7B thermocouple
8 silicon rubber
9 heating plates
10 heaters
11 heater wiring
12A wire
12B wire
13 press
14 cylinders
15 resistance measurement device
16 thermometers
17 transacters
18 temperature controllers

Claims (7)

1. a polyolefin-based porous film, it is the polyolefin-based porous film formed by polyolefin resin composite, and the very big aperture of described polyolefin-based porous film is 0.2-0.5 μm, its aperture surface area is 35.0 ~ 42.0m 2/ g and birefringence is 2.0 × 10 -2~ 4.0 × 10 -2.
2. polyolefin-based porous film according to claim 1, wherein, the porosity of described perforated membrane is 40 ~ 80%.
3. polyolefin-based porous film according to claim 1 and 2, wherein, it is 0.958 ~ 0.965g/cm that polyolefin resin composite contains density 3high density polyethylene (HDPE).
4. a multilayer porous film, it at least comprises the polyolefin-based porous film described in any one of claims 1 to 3.
5. a multi-layer polyolefin system perforated membrane, it has the polyolefin-based porous film described in any one of claims 1 to 3 and at least one refractory layer stacked on the surface at this perforated membrane.
6. multi-layer polyolefin system according to claim 5 perforated membrane, wherein, described refractory layer is made up of the inorganic filler of the fusing point with more than 200 DEG C.
7. a battery separator, it is made up of the perforated membrane described in any one of claim 1 ~ 6 or multilayer porous film.
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